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综述与进展

芳胺对位C(sp2)-H键官能团化研究进展

戴乐薇*,a, 王建玲b, 邹东*,c   

  1. (a浙江中医药大学药学院 杭州 310053)
    (b浙江大学医学院附属第二医院药学部 杭州 310009)
    (c浙江大学医学院附属邵逸夫医院药学部 杭州 310016)
  • 收稿日期:2025-11-25 修回日期:2025-12-22

Recent Advances in the Functionalization of para C(sp²)-H Bonds of Anilines

Lewei Dai*,a, Jianling Wang, Dong Zou*,c   

  1. (aSchool of Pharmaceutical Science, Zhejiang Chinese Medical University, Hangzhou, 310053, Zhejiang, PR China)
    (bDepartment of Pharmacy, The Second Affiliated Hospital Zhejiang University School of Medicine, Hangzhou, 310009, Zhejiang, China)
    (cDepartment of Pharmacy, Sir Run Run Shaw Hospital, College of Medicine, Zhejiang University, Hangzhou, 310016, Zhejiang, China)
  • Received:2025-11-25 Revised:2025-12-22
  • Contact: *E-mail: dailewei0827@163.com, zoudong16@zju.edu.cn

芳胺对位C(sp²)-H键的直接官能团化是有机合成领域中的一个重要研究方向。传统上,实现该位点的选择性官能团化主要依赖于氨基的预保护与活化,此过程不仅步骤繁琐,且严重制约了合成的效率与步骤经济性。近年来,该领域取得了革命性进展,通过发展过渡金属催化、有机光催化、电化学合成以及无金属催化等多元化策略,成功实现了对芳胺对位C-H键的直接、高选择性修饰,从根本上克服了传统方法的局限性。本文旨在系统梳理这一领域的研究脉络,详细总结上述各类催化模式的反应设计、机理特点及其在构建碳-碳与碳-杂原子键中的应用,并对该关键合成转化的发展现状与核心成就进行了全面评述。

关键词: 苯胺, C-H官能团化, 位点选择性, 过渡金属催化, 光催化

The direct functionalization of the para C(sp²)-H bond of anilines represents a significant research direction in organic synthesis. Conventionally, achieving selective functionalization at this position has predominantly relied on the pre-protection and activation of the amino group, a process that is not only step-intensive but also severely limits synthetic efficiency and step economy. In recent years, revolutionary progress has been made in this field. The development of diverse strategies, such as transition metal catalysis, organic photoredox catalysis, electrochemical synthesis, and metal-free catalysis, has successfully enabled the direct and highly selective modification of the para C-H bond of anilines, fundamentally overcoming the limitations of traditional approaches. This review aims to systematically outline the research trajectory in this area, providing a detailed summary of the reaction design, mechanistic characteristics, and applications of these catalytic modalities in constructing carbon-carbon and carbon-heteroatom bonds, thereby offering a comprehensive account of the current development and key achievements in this pivotal synthetic transformation.

Key words: Anilines, C-H Functionalization, Site-Selectivity, Transition Metal Catalysis, Photoredox Catalysis